TWI482850B - High light olefins fcc catalyst compositions - Google Patents

Description

High light olefin fluid catalytic cracking catalyst composition

The present invention relates to catalytic conversion of feedstocks to produce olefins. More specifically, the present invention relates to a novel rhodium-containing catalytic cleavage catalase composition, a process for preparing the catalyst composition, and the use of the catalyst composition to produce a high light olefin yield during the catalytic cracking process.

Catalytic cracking is a petroleum refining process for very large-scale commercial applications. Most refined petroleum products are produced using a fluid catalytic cracking (FCC) process. The FCC process essentially involves cracking a heavy hydrocarbon feedstock into a lighter product by contacting the feedstock in the recycle catalyst recycle cracking process with a circulating fluidizable catalytic cracking catalyst inventory, the catalyst stock being averaged. The particles are comprised of particles between about 20 microns and about 150 microns, preferably between about 50 microns and about 100 microns.

When a relatively high molecular weight hydrocarbon feedstock is converted to a lighter product by catalytic cracking at elevated temperatures in the presence of a catalyst, most of the conversion or cracking occurs in the gas phase. The feedstock is converted to gasoline, distillate, and other liquid cracking products as well as lighter gas cracking products having four or fewer carbon atoms per molecule. This gas portion is composed of olefins and partly composed of saturated hydrocarbons. Bottom and coke are also produced.

In general, product distributions obtainable by modern catalyst cleavage units, particularly fluid catalytic cracking (FCC) units, are acceptable. However, many refiners are looking for improved catalytic cracking processes or processes that increase the amount of light olefin product as well as the amount of gasoline product and octane number. It is also desirable to produce a minimum of bottoms at a fixed or lower coke content.

FCC catalysts are generally composed of many very small spherical particles. Commercial grade particles typically have an average particle size in the range of from about 20 microns to 150 microns, preferably from about 50 microns to about 100 microns. The cracking catalyst is composed of several components that are used to enhance the overall performance of the catalyst. The FCC catalyst is generally composed of a catalytically active zeolite, an active matrix, a clay, and a binder, and combines all the components into a single particle. Alternatively, the catalyst is composed of a blend of various particles having different functions.

FCC catalysts containing rare earth exchanged zeolites have been widely used commercially, and their general technical properties are also widely known. See Fluid Catalytic Cracking with Zeolite Catalysts, Venuto and Habib, 1979 Marcel Dekker, pp. 30-46. In addition, FCC catalysts containing rare earth exchanged Y-type zeolites have been disclosed in a number of patents, including U.S. Patent No. 3,436,357 and U.S. Patent No. 3,930,987.

U.S. Patent No. 4,405,443 discloses the exchange of rare earth-exchanged zeolite followed by mixing with cerium and an inorganic oxide to produce an absorbent for oxidizing sulfur.

U.S. Patent No. 4,793,827 discloses a hydrocarbon cracking catalyst comprising a rare earth exchanged Y-type zeolite which has been ion exchanged to enhance the rhodium content of the catalyst.

U.S. Patent No. 5,908,547 discloses a cerium-containing zeolite Y-type catalyst which is substantially free of rare earth ions.

Brief description of the invention

It has been found that the rhodium-containing catalyst composition provides a high yield of light olefins compared to conventional rhodium-containing catalytic cracking catalysts. In particular, the catalytic cracking catalyst is a fluid catalytic cracking (FCC) catalyst. The catalyst composition of the present invention is based on a zeolite catalytic component which has catalytic cracking activity under catalytic cracking conditions, preferably a Y-type zeolite which has been deuterium and at least one rare earth metal other than cerium. Combination ratio exchange. Advantageously, compared with a conventional light olefin yield of the obtained lanthanum Y- type zeolite FCC catalyst, according to the present invention containing yttrium / rare FCC catalyst C can provide higher yields during the FCC process to ₂ C ₄ light olefin. Surprisingly, the rhodium/rare earth catalyst composition of the present invention provides higher gasoline olefin yield and bottoms conversion while maximizing light olefin yield.

Accordingly, it is an advantage of the present invention to provide novel rhodium-containing catalyst compositions which promote high light olefin yields during the catalyst cracking process, particularly the FCC process.

Still another advantage of the present invention is to provide a novel FCC catalyst composition having a specific combination of ruthenium and at least one rare earth metal that promotes high yields of light olefins during the FCC process.

Still another advantage of the present invention is to provide a FCC catalyst composition comprising cerium and a rare earth metal which promotes an increase in gasoline olefins during the catalyst cracking process, thereby resulting in a higher octane number of the gasoline product.

Another advantage of the present invention is the provision of a high light olefin containing rhodium/rare earth FCC catalyst composition which improves the bottoms conversion during the FCC process.

Still another advantage of the present invention is to provide a low lanthanum and rare earth-containing FCC catalyst composition that incorporates a ZSM-5 light olefin additive as compared to a ruthenium containing FCC catalyst conventionally incorporating a ZSM-5 light olefin additive. It promotes higher light olefin and gasoline olefin production.

Still another advantage of the present invention is to provide a process for preparing the rhodium/rare earth-containing FCC catalyst of the present invention.

Still another advantage of the present invention is to provide a method of increasing the yield of light olefins produced during the FCC process by using the rhodium/rare earth catalyst composition of the present invention.

Still another advantage of the present invention is to provide a process for increasing the yield of light olefins during the FCC process while at the same time increasing gasoline olefin yield and bottoms conversion.

Still another advantage of the present invention is to provide an improved FCC process using the compositions and methods of the present invention.

These and other aspects of the invention are described in more detail below.

Description of the invention

The discovery of the present invention is that a relatively small amount of rhodium and rare earth are exchanged over the zeolite cracking component, which provides a catalyst composition having the ability to produce a higher yield of light olefins during the FCC process under catalytic cracking conditions. It has catalytic cracking activity, especially under fluid catalytic cracking (FCC) conditions. It has been found that the exchange of rhodium and rare earth at a specific relative ratio on the catalytically cracked active zeolite enhances the effect of increasing the yield of light olefins while maximizing the yield of gasoline olefins.

For purposes of this invention, as used herein, "light olefins" means ethylene term C ₂ to C ₄ olefins such as ethylene, propylene and butylene.

For purposes of this invention, "Olefin" as used herein, refers to the word B C ₅ to C ₁₂ olefins, which increases the octane number of the gasoline product.

Niobium is a metal commonly found in rare earth minerals and is occasionally referred to as rare earth metals. To be clear, cockroaches are not considered to be a rare earth metal. The atomic order of ruthenium is 39, and therefore is not among the rare earths of the periodic table, which has an atomic order of 57 to 71. Metals having an atomic order within this range include ruthenium (atomic sequence 57) and lanthanide metals. See Hawley's Condensed Chemical Dictionary, 11th Edition (1987). Therefore, the term "rare earth" or "rare earth metal" as used hereinafter means a lanthanum having an atomic order of 57 in the periodic table, a lanthanide metal having an atomic order of 58 to 71 in the periodic table, and its corresponding oxide and Its combination. In general, the rare earth metal is a metal selected from the group consisting of ruthenium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, and combinations thereof.

As used herein, the term "anthracene compound" refers not only to the oxime (e.g., sulfonium salt) in the form of a compound, but also to the form of a phosphonium cation, such as a phosphonium cation exchanged on a zeolite. Unless otherwise mentioned, the words "钇 compound" and "钇" will be used interchangeably. Unless otherwise indicated herein, the weight measurement of the ruthenium or osmium compound is carried out by elemental analysis techniques conventionally used in the art and is described in the form of yttrium oxide (Y ₂ O ₃ ). Analytical techniques include, but are not limited to, inductively coupled plasma (ICP) analysis.

For the purposes of the present invention, the terms "cerium/rare earth catalyst composition" and "rhenium/rare earth catalyst" are used interchangeably herein to indicate the catalyst composition of the present invention containing cerium and rare earth.

The zeolite cracking component which can be used in the composition of the present invention can be any zeolite having catalytic cracking activity under catalytic cracking conditions, particularly under fluid catalytic cracking conditions. Zeolite components suitable for this purpose include a wide variety of zeolites. Suitable zeolites include macroporous crystalline yttrium aluminate zeolites such as synthetic faujasites, i.e., Y-type zeolites, X-type zeolites, and beta zeolites, as well as heat treated (calcined) derivatives thereof. The zeolite cracking component is preferably a synthetic faujasite such as a Y zeolite. The zeolite is preferably an ultra-stable Y-type zeolite (USY) as disclosed in U.S. Patent No. 3,293,192.

It is also within the scope of the invention to utilize zeolites such as kaolin or metakaolin clay to synthesize zeolite cleavage components. For example, the zeolite can be a zeolite produced by treating clay with a citrate source under alkaline conditions. A method of making such a zeolite is known and is described in U.S. Patent No. 3,459,680, the disclosure of which is incorporated herein by reference. Other methods of making zeolites from clay have also been disclosed in U.S. Patent Nos. 4,493,902 and 6,656,347, the disclosures of each of each of each

According to the invention, the zeolite cracking component is exchanged by a combination of rhodium and at least one rare earth. In a conventional manner, rhodium and rare earths can be exchanged separately or simultaneously on the zeolite. In a preferred embodiment, the ruthenium is directly exchanged on the zeolite prior to the addition of any optional ingredients. This embodiment can be carried out in an aqueous exchange bath containing a water-soluble cerium salt. Suitable water soluble salts include hydrazine halides (e.g., chlorides, bromides, fluorides, and iodides), nitrates, sulfates, carbonates, and acetates. The concentration of the water soluble salt used in this example must be sufficient to provide the desired rhodium concentration on the zeolite. The ruthenium compound may consist essentially of ruthenium or the ruthenium compound may comprise ruthenium and rare earth containing moieties. In addition to this, rare earths can be used in aqueous exchange baths containing water-soluble rare earth salts such as halides (such as chlorides, bromides, fluorides and iodides), nitrates, sulfates, carbonates and acetates. Exchanged separately on the zeolite.

The amount of rhodium exchanged on the zeolite cracking component is generally between about 1.75 wt% and about 0.175 wt% of the zeolite. The amount of rhodium exchanged on the zeolite is preferably between about 1.50% and about 0.20% by weight of the zeolite; most preferably between about 1.40% and about 0.30% by weight of the zeolite. Generally, the ratio of ruthenium exchanged on the zeolite relative to the rare earth metal is from 3 to 50, preferably from 3.5 to 20. As will be appreciated by those skilled in the art, the amount of rare earth exchanged on the zeolite will vary with the amount of rhodium exchanged on the zeolite and the desired ratio of rhenium to the rare earth. For example, when the zeolite is exchanged at 1.75 wt% ruthenium and the ratio of ruthenium to rare earth metal is from 3 to 50, the amount of rare earth exchanged on the zeolite will range from about 0.583 wt% to about 0.035 wt%. However, the total amount of rhodium and rare earth typically exchanged on the zeolite cracking component is in the range of about 2.33 wt% or less, preferably from about 0.20 wt% to about 2.0 wt%.

This cerium/rare earth exchanged zeolite cracking component can also be exchanged by a combination of metal and ammonium and/or acid ions. The zeolite component may also comprise a mixture of zeolites, such as synthetic faujasite in combination with mordenite and ZSM-type zeolite. In general, the zeolite cracking component constitutes from about 10% to about 60% by weight of the cracking catalyst. The rhodium/rare earth exchanged zeolite cracking component preferably constitutes from about 20% to about 50% by weight of the catalyst composition, most preferably from about 30% to about 55% by weight.

The catalyst of the present invention may also optionally include a filler such as clay. Although kaolin is a preferred clay component, it is also contemplated that other clays, such as modified kaolin (e.g., metakaolin), may optionally be included in the catalyst of the present invention. When used, the clay component will generally comprise from about 10% to about 90% by weight of the catalyst composition, preferably from about 20% to about 80% by weight, and most preferably from about 30% to about 70% by weight. .

The catalyst composition of the present invention may also optionally comprise at least one or more matrix materials. Matrix materials suitable for selective appearance in the catalyst of the present invention include, but are not limited to, aluminum oxide, cerium oxide, cerium aluminum oxide, and combinations thereof. The matrix material content in the catalyst of the present invention is from about 10% by weight to about 90% by weight, preferably from about 30% by weight to about 70% by weight, based on the weight of the catalyst composition. It is also within the scope of the invention for the matrix material to contain a binder at the same time. Suitable binders include, but are not limited to, cerium oxide sol, alumina sol, sodium citrate, peptized alumina, and combinations thereof. The binder is typically present in an amount from about 5% by weight to about 30% by weight based on the weight of the catalyst composition.

The catalyst composition of the present invention can be used in combination with other additives conventionally used in catalytic cracking processes, particularly FCC processes, which are still within the scope of the present invention, such as SOx reduction, NOx reduction, gasoline reduction Content additives, CO combustion promoters, additives for the manufacture of light olefins, and the like.

In a preferred embodiment of the invention, the rhodium/rare earth catalyst of the present invention is used in combination with separate ZSM-5 light olefin additive particles. Any of the conventional ZSM-5 light olefin additives conventionally used in the FCC process for light olefin production can be used in the present invention. Generally, these additives include particles having a size between about 20 microns and about 150 meters, preferably from about 50 microns to about 100 microns, and containing from about 10% to about 50% by weight of ZSM-5. Alternatively, these additives may further comprise a matrix, a binder and/or a clay. Preferred ZSM-5 light olefin additives include, but are not limited to, and It is manufactured and sold by the Grace Davision division of WR Grace & Co.-Conn., Columbia, Maryland. Other ZSM-5-containing additives useful in the present invention for the manufacture of light olefins include, but are not limited to, the following additives, under the trade name Z-CAT , , Z-CAT HP ^TM , , ^{, PENTACAT TM, PROPLYMAX TM, ISOCAT} HP TM, SUPER Z TM, PENTACAT HP TM, PENTACAT PLUS TM, OCTAMAX TM, OCTAMAX HP TM, K-1000 TM, K-2000 TM, BOOST TM, IsoBOOST TM and MOA ^TM. In a preferred embodiment of the invention, the ZSM-5 additive is a phosphorus-stable ZSM-5 additive, as disclosed in U.S. Patent No. 6,916,757, the disclosure of which is incorporated herein by reference. The ZSM-5 light olefin additive is preferably used in an amount ranging from about 0.2% by weight to about 30% by weight based on the weight of the catalyst composition.

The particle size and attrition properties of the catalyst of the present invention affect the fluidization properties in the catalytic cracking unit and will determine the extent to which the catalyst remains in this commercial unit, particularly in the FCC unit. The catalyst composition of the present invention has an average particle size of from about 20 microns to about 150 microns, more preferably from 50 microns to 100 microns. The abrasion properties of the catalyst of the present invention are expressed in terms of the Davison Attrition Index (DI), which is generally less than 20, more preferably less than 10, and most preferably less than 8.

The catalyst composition of the present invention is prepared by forming an aqueous slurry comprising 30 to 50 parts by weight of a cerium/rare earth exchanged zeolite cracking component, and optionally, from about 0 to about 70% by weight of clay, matrix. And binder materials. The aqueous slurry is ground to obtain a uniform or substantially uniform slurry. Alternatively, the slurry forming ingredients are ground prior to forming the slurry. The slurry is then mixed to obtain a uniform or substantially uniform aqueous slurry.

The aqueous slurry is then subjected to a spray drying step using conventional spray drying techniques. In a preferred embodiment, the slurry is spray dried at a spray dryer inlet temperature of between about 220 ° C and about 370 ° C and a spray dryer outlet temperature of between about 135 ° C and about 180 ° C. . The spray dried catalyst can be used directly as a finished catalyst or calcined prior to use. When calcined, the catalyst particles are calcined in a temperature range of from about 250 ° C to about 800 ° C for from about 4 hours to about 10 seconds. The catalyst particles are preferably calcined in a temperature range of from about 350 ° C to about 600 ° C for from about 2 hours to about 10 seconds.

The rhodium/rare earth-containing cracking catalyst composition of the present invention is particularly useful for the FCC process, which provides a higher yield of light olefins than conventional cracking catalyst compositions based on rhodium-exchanged zeolite catalytic cracking of the active ingredient. The use of the catalyst of the present invention results in an increase in light olefin yield of up to about 15%, preferably from about 0.7% to about 12%, as compared to a FCC catalyst composition based on ytterbium exchanged Y zeolite. The rhodium/rare earth catalyst composition of the present invention is advantageous for increasing the yield of light olefins while at the same time increasing the yield of gasoline olefins, thereby increasing the octane number of the gasoline product obtained. Further, by using the cerium/rare earth-containing catalyst composition of the present invention, the conversion of the bottoms can be increased during the FCC process.

For the purposes of the present invention, the term "catalytic cracking conditions" as used herein refers to the conditions of a typical catalytic cracking process, which is almost the FCC process, in which the cyclic inventory of the catalytic cracking catalyst is contacted with the heavy hydrocarbon feedstock at elevated temperatures. The starting material is converted to a lower molecular weight compound.

As used herein, the term "catalytic cleavage activity" refers to the ability of a zeolite to catalyze the conversion of a hydrocarbon to a lower molecular weight compound under catalytic cracking conditions, particularly under conditions of fluid catalytic cracking.

The cracking catalyst composition of the present invention is particularly useful in conventional FCC processes or other catalytic cracking processes in which a hydrocarbon feedstock is cleaved into lower molecular weight compounds. Slightly speaking, FCC conditions involve the cracking of heavy hydrocarbon feedstocks to form lower molecular weight hydrocarbon components, which are the fluidized catalytic cracking catalysts in the circulating catalyst recycling cracking process at elevated temperatures and cycles. In stock contact, the catalyst inventory is comprised of particles having an average particle size between about 20 microns and about 150 microns, preferably between about 50 microns and about 100 microns. Catalytic cracking of these relatively high molecular weight hydrocarbon feedstocks will result in the formation of lower molecular weight hydrocarbon products. The important steps of the cyclic FCC method are:

(i) catalytic cracking in a catalytic cracking zone (typically a riser cracking zone) in which the feed is operated under catalytic cracking conditions by contacting the feed with a hot regenerated cracking catalyst source to produce an effluent, It comprises a cracking product and a catalyst for containing coke and a strippable hydrocarbon;

(ii) discharging the effluent and (generally in one or more cyclones) a vapor phase enriched in the cracking product and a solid phase rich in the catalyst;

(iii) taking the vapor phase as a product and fractionating the FCC main column and its accompanying secondary column to form a gas and liquid cracking product comprising gasoline;

(iv) stripping the used catalyst, usually in steam, to remove the trapped hydrocarbons from the catalyst, and then regenerating the stripped catalyst in the catalyst regeneration zone to produce The hot regenerative catalyst is then recycled to the cracking zone for cracking a greater amount of feed.

A typical FCC process is carried out at a reaction temperature of from about 480 ° C to about 570 ° C, preferably from about 520 ° C to about 550 ° C. The reactor effluent containing hydrocarbon vapors and a cracking catalyst containing carbonaceous material or coke is transferred to a separation zone where the spent cracking catalyst is removed from the hydrocarbon vapor and prior to regeneration It is stripped in the stripping zone. The stripping zone may suitably be maintained at a temperature in the range of from about 470 ° C to about 560 ° C, preferably from about 510 ° C to about 540 ° C.

The temperature of the regeneration zone will vary with the particular FCC unit. As will be understood by those skilled in the art, the catalyst regeneration zone can be comprised of a single or multiple reaction vessels. The regeneration zone temperature is generally in the range of from about 650 ° C to about 760 ° C, preferably from about 700 ° C to about 730 ° C.

The cracking catalyst compositions of the present invention can be added to the recycled FCC catalyst stock during the cracking process, or they can be present in the inventory at the start of the FCC operation. As will be appreciated by those skilled in the art, these catalyst particles can also be added directly to the lysis zone, the regeneration zone of the FCC cleavage apparatus, or any other suitable location in the FCC process.

It is within the scope of the invention to use the cracking catalyst composition of the present invention alone or in combination with other conventional FCC catalysts, including, for example, zeolite catalysts having a faujasite cracking component. , for example, Venuto and Habib, as described in the Basic Review of Fluid Catalytic Cracking with Zeolite Catalysts , Marcel Dekker, New York, 1979, ISBN 0-8247-6870-1, and in many other sources, such as Sadeghbeigi, Fluid Catalytic Cracking Handbook , Houston's Gulf Publishing Company, 1995, ISBN 0-88415-290-1. The FCC catalyst is usually composed of a binder (usually cerium oxide, aluminum oxide or yttrium aluminum oxide), an active component of the Y-type zeolite acidic site, one or more matrix alumina and/or yttrium aluminum oxide, and clay (such as kaolin clay). Composition.

The ruthenium/rare earth catalyst of the present invention can be used to crack any typical hydrocarbon feedstock including, but not limited to, hydrotreated feedstock, vacuum gas oil (VGO), residual oil, atmospheric column bottoms, petroleum coke Gas oil and its combination.

The following specific examples are presented to further illustrate the invention and its advantages. The examples provided are specific illustrations of the invention. However, it should be understood that the invention is not limited to the specific details of the embodiments.

All parts and percentages referred to in these examples, as well as in the remainder of this patent application, relating to solid compositions or concentrations are by weight unless otherwise indicated. However, unless otherwise stated, all parts and percentages of the gas compositions referred to in these examples, as well as the remainder of this patent application, are based on moles or volumes.

In addition, any numerical range recited in the application or the scope of the application, such as a particular combination of the properties, the unit of measurement, the condition, the physical state, or the percentage, is meant to be explicitly recited herein by reference, or included Any subset of any number within any range recited, any number falling within the scope.

Example

As used herein, "CPS" refers to a cyclic propylene vapor deactivation procedure that stimulates the REDOX process by using propylene and air in addition to the steam deactivation effect (see American Chemical Society Proceedings Series, Volume 634). , pp. 171-183 (1996)).

As used herein, "ACE" refers to the advanced lysis evaluation test described in U.S. Patent No. 6,069,012, the disclosure of which is incorporated herein by reference.

The surface area shown herein is measured by the N ₂ BET method and chemical analysis is performed by ICP analysis in accordance with the standards of the National Institute of Standards and Technology.

As used herein, "DCR" refers to a Davison cyclic riser. The description of DCR was published in the following papers: GW Young, GD Weatherbee and SW Davey, "Simulating Commercial FCCU Yields with the Davison Circulating Riser Pilot Plant Unit"", National Petroleum Refining Industry Association (NPRA) Document No. AM88-52; GW Young, "Realistic Assessment of FCC Catalyst Performance in the Laboratory", Fluid Catalytic Cracking: Science and Techology, JS Magee and MM Mitchell, Jr., ed., Studies in Surface Science and Catalysis, Vol. 76, p. 257, Elsevier Science Publishers BV Publishing, Amsterdam 1993, ISBN 0-444-89037-8.

Example 1

The base catalyst was prepared in the following manner: Catalyst A: 6954 g (dry basis: 1919 g), low base USY, 3478 g (dry basis: 800 g) of aluminum hydroxychloride, 947 g (dry basis 500) A) alumina, and 2118 grams (1800 grams of dry basis) clay, and 370 grams (100 grams of dry basis) aqueous solution of the lanthanide solution, and mixed for about 10 minutes to form an aqueous slurry. The slurry was ground in a Drais mill to reduce particle size and spray dried in a Bowen spray dryer with an inlet temperature of 343 °C. The spray dried particles were calcined at 1100 °F (593 °C) for 1 hour. The chemical and physical properties of the catalyst are shown in Table 1 below.

Example 2

The catalyst of the present invention was prepared in the following manner: Catalyst B: 6954 g (dry basis: 1919 g) of low base USY, 3478 g (dry basis: 800 g) of aluminum hydroxychloride, 947 g (dry basis) 500 g) alumina, and 2118 g (1800 g dry basis) clay, and 77 g (dry basis 17.6 g) hydrazine concentrated solution were mixed and mixed for about 10 minutes to form an aqueous slurry. The slurry was ground in a Drais mill to reduce particle size and spray dried in a Bowen spray dryer with an inlet temperature of 343 °C. The spray dried particles were calcined at 1100 °F (593 °C) for 1 hour. The chemical and physical properties of the catalyst are shown in Table 1 below.

Example 3

The catalyst of the present invention was prepared in the following manner. Catalyst C: 5856 g (dry basis: 1616 g) of low base USY, 3043 g (700 g of dry basis) of aluminum hydroxychloride, 947 g (dry basis) were sequentially added. 500 g) of alumina, and 2588 g (2200 g of dry basis) clay, and an aqueous solution of 77 g (dry basis of 17.6 g) of cerium concentrated solution, and mixed for about 10 minutes to form an aqueous slurry. The slurry was ground in a Drais mill to reduce particle size and spray dried in a Bowen spray dryer with an inlet temperature of 343 °C. The spray dried particles were calcined at 1100 °F (593 °C) for 1 hour. The chemical and physical properties of the catalyst are shown in Table 1 below.

Example 4

The ability of catalysts A, B, and C to increase light olefins during the FCC process was evaluated. The catalyst was deactivated at 1450 °F (788 °C) for 20 hours using CPS. After deactivation, ACE was used to test the catalyst.

For evaluation, commercial FCC feeds were used as described in Table 2 below.

The results are reported in Table 3 below.

The results in Table 3 show that the ruthenium-containing/rare earth catalysts (catalysts B and C) of the present invention produce increased amounts of C ₃ and C ₄ light olefins compared to the ruthenium-containing base catalyst (catalyst A). Gasoline olefins.

Example 5

The base catalyst was prepared in the following manner: Catalyst D: 8418 g (dry basis is 2323 g) low base USY, 3696 g (dry basis 850 g) aluminum hydroxychloride, 379 g (dry basis 200) A) alumina, and 1941 grams (1650 grams of dry basis) clay, and 222 grams (60 grams of dry basis) aqueous solution of the lanthanide solution, and mixed for about 10 minutes to form an aqueous slurry. The slurry was ground in a Drais mill to reduce particle size and spray dried in a Bowen spray dryer with an inlet temperature of 343 °C. The spray dried particles were calcined at 1100 °F (593 °C) for 1 hour. The chemical and physical properties of the catalyst are shown in Table 4 below.

Example 6

The catalyst of the present invention was prepared in the following manner. Catalyst E: 8418 g (dry basis: 2323 g) of low base USY, 3696 g (dry basis: 850 g) of aluminum hydroxychloride, 379 g (dry basis) were sequentially added. 200 g) alumina, and 1941 g (dry basis is 1650 g) clay, and 92 g (dry basis 21.0 g) hydrazine concentrated solution, and mixed for about 10 minutes to form an aqueous slurry. The slurry was ground in a Drais mill to reduce particle size and spray dried in a Bowen spray dryer with an inlet temperature of 343 °C. The spray dried particles were calcined at 1100 °F (593 °C) for 1 hour. The chemical and physical properties of the catalyst are shown in Table 4 below.

Example 7

The catalyst of the present invention was prepared in the following manner. Catalyst F: 8418 g (dry basis: 2323 g) of low base USY, 3696 g (dry basis: 850 g) of aluminum hydroxychloride, 379 g (dry basis) was added. 200 g) of alumina, and 1941 g (1,450 g of dry basis) clay, and 46 g (10.5 g of dry basis) of an aqueous solution of concentrated solution were mixed for about 10 minutes to form an aqueous slurry. The slurry was ground in a Drais mill to reduce particle size and spray dried in a Bowen spray dryer with an inlet temperature of 343 °C. The spray dried particles were calcined at 1100 °F (593 °C) for 1 hour. The chemical and physical properties of the catalyst are shown in Table 4 below.

Example 8

The ability of catalysts E, F and D to increase light olefins during the FCC process was evaluated. The catalyst was deactivated at 1450 °F (788 °C) for 20 hours using CPS. After deactivation, ACE was used to test the catalyst.

For evaluation, commercial FCC feeds were used as described in Table 2.

The results are reported in Table 5 below.

The results in Table 5 show that the ruthenium-containing/rare earth catalysts (catalysts E and F) of the present invention produce increased amounts of C ₃ and C ₄ light olefins compared to the ruthenium-containing base catalyst (catalyst D). Gasoline olefins.

Example 9

The catalyst was prepared in the following manner. Comparing the catalyst G: 7869 g (dry basis was 2171 g), low base USY, 3696 g (dry basis 850 g) of aluminum hydroxychloride, and 2352 g (dry basis) were added. 1999 g) clay, and 35 g (dry basis 8.0 g) aqueous solution of pure hydrazine solution, and mixed for about 10 minutes to form an aqueous solution. The slurry was ground in a Drais mill to reduce particle size and spray dried in a Bowen spray dryer with an inlet temperature of 343 °C. The spray dried particles were calcined at 1100 °F (593 °C) for 1 hour. The chemical and physical properties of the catalyst are shown in Table 6 below.

Example 10

The catalyst was prepared in the following manner: Catalyst H: 7869 g (dry basis was 2171 g), low base USY, 3696 g (dry basis 850 g) of aluminum hydroxychloride, and 2352 g (dry basis 1999) were added. G) clay, and 35 g (dry basis 8.0 g) aqueous solution of concentrated solution, and mixed for about 10 minutes to form an aqueous slurry. The slurry was ground in a Drais mill to reduce particle size and spray dried in a Bowen spray dryer with an inlet temperature of 343 °C. The spray dried particles were calcined at 1100 °F (593 °C) for 1 hour. The chemical and physical properties of the catalyst are shown in Table 6 below.

Example 11

The comparative catalyst G prepared in Example 9 and the catalyst H prepared in Example 10 were evaluated for their ability to increase light olefins during the FCC process. The catalyst was deactivated at 1465 °F (796 °C) for 20 hours using CPS. After deactivation, ACE was used to test the catalyst.

For evaluation, commercial FCC feeds were used as described in Table 2 above.

The results are reported in Table 7 below.

The results in Table 7 show that the ruthenium/rare earth catalyst (catalyst H) of the present invention produces increased amounts of C3 and C4 light olefins and gasoline olefins compared to the comparative catalyst G which does not contain rare earths but contains only ruthenium.

Example 12

Comparative catalyst G prepared in Example 8 and 4% by weight of Olefins Ultra Blending, a commercial olefin additive containing ZSM-5, manufactured and sold by Grace Davision, WR Grace & Co.-Conn., Columbia, Maryland.

Example 13

Comparative catalyst H prepared in Example 9 and 4% by weight of Olefins Ultra Blending, a commercial olefin additive containing ZSM-5, manufactured and sold by Grace Davision, WR Grace & Co.-Conn., Columbia, Maryland.

Example 14

The catalyst blends prepared in Example 12 and Example 13 were evaluated for their ability to increase light olefins during the FCC process. These blends were deactivated at 1465 °F (788 °C) for 20 hours using CPS. After deactivation, ACE was used to test the catalyst.

For evaluation, commercial FCC feeds were used as described in Table 2 above.

The results are reported in Table 8 below.

The results in Table 8 show, compared with only blending of yttrium-containing catalyst of Comparative G and ZSM-5 additive is used in conjunction with the present invention yttrium ZSM-5 additive / rare earth catalyst may produce an increased number of C ₃ and C ₄ light olefins and gasoline olefins.

Example 1 5

Comparative catalyst I was prepared as follows: 6954 g (1919 g dry basis) low base USY, 3478 g (dry basis 800 g) aluminum hydroxychloride, 947 g (500 g dry basis) were added. Aluminum, and 2118 grams (1800 grams of dry basis) clay, and 307 grams (70.0 grams of dry basis) of aqueous solution of concentrated solution, and mixed for about 10 minutes to form an aqueous slurry. The slurry was ground in a Drais mill to reduce particle size and spray dried in a Bowen spray dryer with an inlet temperature of 343 °C. The spray dried particles were calcined at 1100 °F (593 °C) for 1 hour. The chemical and physical properties of the catalyst are shown in Table 9 below.

Example 16

The base catalyst A prepared in Example 1, the comparative catalyst I prepared in Example 15, and the catalyst B prepared in Example 2 were evaluated for their ability to increase light olefins during the FCC process. These blends were deactivated at 1450 °F (788 °C) for 20 hours using CPS. After deactivation, ACE was used to test the catalyst.

For evaluation, commercial FCC feeds were used as described in Table 2 above.

The results are reported in Table 10 below.

The results in Table 10 show that the comparative catalyst I having a cerium concentration greater than 1.75 wt% produced less than the catalyst B of the present invention having a cerium concentration of from about 1.75 wt% to about 0.175 wt%, based on the weight of the zeolite. C ₃ and C ₄ and gasoline olefins.

Claims (16)

A catalyst composition for catalytically cracking hydrocarbons to maximize light olefin production, the composition comprising a zeolite having catalytic cracking activity under catalytic cracking conditions, the zeolite being exchanged with at least one rare earth metal, Wherein the amount of rhodium exchanged on the zeolite is from about 1.75 wt% to about 0.175 wt% of the zeolite, and the ratio of rhodium exchanged on the zeolite to the rare earth metal is from about 3 to about 50. The catalyst of claim 1, wherein the zeolite is a faujasite. A catalyst according to claim 3, wherein the zeolite is a Y-type zeolite. A catalyst according to claim 1, wherein the rare earth metal is a metal selected from the group consisting of ruthenium, a periodic metal such as an atomic number of 58 to 71, and a combination thereof. The catalyst of claim 1, wherein the zeolite content in the catalyst is from about 10% to about 60% by weight of the catalyst composition. The catalyst of claim 5, wherein the zeolite content in the catalyst is from about 20% to about 50% by weight of the catalyst composition. The catalyst of claim 1, wherein the ratio of ruthenium exchanged on the zeolite to the rare earth is from about 3.5 to about 20. For example, the catalyst of claim 1 of the patent scope, wherein the catalyst also contains clay. The catalyst of claim 1, wherein the catalyst further comprises at least one ZSM-5 light olefin additive. For example, the catalyst of claim 9 wherein the ZSM-5 light olefin additive comprises a phosphorus stabilized ZSM-5 additive. The catalyst of claim 1, wherein the zeolite has catalytic cracking activity under fluid catalytic cracking conditions. A method for catalytically cracking a hydrocarbon feedstock to a lower molecular weight component to maximize light olefin production, the method comprising contacting a hydrocarbon feedstock with a cracking catalyst at elevated temperatures to form a lower molecular weight hydrocarbon component, the cracking The catalyst comprises (a) a composition as set forth in claims 1, 3, 7 and 9. The method of claim 12, wherein the cracking catalyst further comprises faujasite. The method of claim 13, wherein the zeolite is a Y-type zeolite. The method of claim 12, further comprising recovering the cracking catalyst from the contacting step and treating the spent catalyst in the regeneration zone to regenerate the catalyst. The method of claim 12, wherein the hydrocarbon feedstock is contacted with the cracking catalyst under fluid catalytic cracking conditions.